Structural Evidence for Aromatic Heterocycle N–O Bond Activation via Oxidative Addition

08 November 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Many methods report the scission of the N–O bonds of aromatic heterocycles and their subsequent functionalization. Oxidative addition is one of the presumed pathways through which aromatic N–O bond activation with transition metals is achieved. We report the first well-defined pathway of (benz)isoxazole’s aromatic N–O bond activation through oxidative addition. We also provide control experiments which show that aromatic N–O bonds may be broken by strong inorganic reductants. These results highlight that N–O bonds are susceptible to both reduction and oxidative addition, which has important implications for catalysis. Exploring the reactivity of one of these complexes towards a series or electrophiles led to the discovery of a Staudingertype β-lactam synthesis upon reaction with a ketene. Finally, we demonstrate that choice of different metal/ligand combinations allows for selective oxidative addition into either C–I bonds or N–O bonds in the presence of the other.

Keywords

nickel
heterocycles
oxidative addition
N-O bond

Supplementary materials

Title
Description
Actions
Title
SI
Description
SI
Actions

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.